Xiaofan He, Xiao Liang, Jiaying Yu, Jie Rong, Jinzhong Hu, Chensen Xu, Zhuoer Cai, Jian Chen, Yinan Zhang, Xin Pu, Pengfei Sun, Hsin-Mao Wu, Bo Sun
Conventional antibody- or peptide–drug conjugates (ADCs/PDCs) improve tumor selectivity, yet the unimolecular integration of imaging guidance and multimodal therapy remains limited. Here, we introduce a peptide–photosensitizer–drug conjugate (P 2 DC) strategy that enables unified NIR-II imaging and synergistic multimodal therapy. As a proof of concept, a hypoxia-activated prodrug, IT-azo-RGD, is constructed by integrating a computationally optimized photosensitizer core, a hypoxia-cleavable azo linker bridging a drug payload, and bis-cRGDfK for multivalent integrin targeting. Theoretical calculations reveal that the active photosensitizer core (IT-m-NH 2 ) exhibits bright NIR-II fluorescence, efficient photothermal conversion, and type-I photodynamic reactivity, while also elucidating the mechanisms underlying IT-azo-RGD self-assembles into nanospheres that undergo hypoxia-triggered disassembly upon drug release. IT-azo-RGD displays triple tumor targeting through integrin affinity, EPR-mediated accumulation, and hypoxia activation. Upon azo cleavage, • OH generation increases by approximately 6-fold, and the photothermal efficiency reaches 59.7%. These features support NIR-II imaging-guided chemo-photothermal-photodynamic synergy. In the orthotopic osteosarcoma mouse model, IT-azo-RGD achieves 97.7% tumor inhibition, suppresses lung metastasis, and shows no systemic toxicity. This P 2 DC concept provides a generalizable design framework for a unimolecular theranostic prodrug.